1, 4-diamino-2, 3-anthraquinonedicarboxamides



Patented Oct. 19, 1954 1,4-DIAMINO-2,3-ANTHRAQUINONE- DICARBOXAMIDESMelvin A. Perkins, Wilmington, Del., assignor to E. I. du Pont deNemours and Company, Wil-- mington, Del., a corporation of Delaware NoDrawing. Application December 5, 1951 Serial No. 260,085

Claims. 1

This invention relates to the preparation of new compounds, moreparticularly 1,4-diamino-2,3 anthraquinone-dicarboxamides, which areespecially useful as dyes for the new polyethylene terephthalate fiberknown generally as Dacron fiber.

As pointed out in the J. Soc. Dyers & Colourists, 1946, page 348, thediscovery of dyes which are suitable for the coloring of the newpolyethylene terephthalate fiber, and the various methods for theapplication of these dyes, has presented a real problem. See alsoAmerican Dyestuff Reporter, 1948, page 699. Blue dyes of satisfactoryapplication and fastness properties have been particularly diflicult tofind for use not only in the dyeing of this new fiber but in the dyeingof many of the older and now commonly used fibers, and the need for ablue dye for this new polyethylene terephthalate fiber has beendiscussed in the American Dyestuff Reporter of January 1951, page 54,under the dyeing of Fiber V.

It is an object of the present invention to provide new compounds of theanthraquinone series, and more particularly l,4-diamino-2,3-anthraquinone-dicarboxamides, which are applicable to the coloring of thenew polyethylene terephthalate fibers now known as Dacron.

The new compounds of the present invention have the following generalformula:

(H) NHz CONR:

CONR2 in which the Rs on the amide nitrogens stand for substituents ofthe group consisting of -H, -alkyl and -hydroxyalkyl, the total numberof carbon atoms in both Rs attached to a single amide nitrogen being notmore than four.

The following examples are given to illustrate this invention. The partsused are by weight.

Example 1 A mixture of 17 parts of1,4-diamino-2,3-anthraquinone-dicarboxylic acid, 150 parts ofnitrobenzene and 42 parts of thionyl chloride was heated with stirringto 125 C. and kept at 125 C. for 2 hours. The blue solution became red.Dried air was passed through the solution for 20 minutes and thetemperature was lowered to 90 C. Ammonia gas was passed through thesolution at 90 C. until no more ammonia was adsorbed, and the mixturewas stirred at 90 C.

2 for an additional hour. The solution was cooled to room temperatureand 250 parts of alcohol was added to precipitate the dye. The dye wasseparated by filtration and washed with alcohol and then hot water anddried. The 1,4-diamino-2,3'- anthraquinone-dicarboxamide of the formula:

(I) NHB C ONRz C ONRa 9) NH: obtained has a melting point over 300 C.and dyes Dacron fiber in greenish-blue shades having goodlight-fastness.

Example 2 1 ,4-diamino-N,N -bis 2-hydroxyethyl) -2 ,3-anthraquinone-dicarboxamide was prepared by the method of Example 1from 17 parts of 1,4-diamino-2,3-anthraquinone-dicarboxylic acid, 150parts of nitrobenzene, 42 parts of thionyl chloride and parts ofethanolamine. The carboxamide compound of the formula:

IO NHQ CONH(CH:)2OH

CONH(CH2)2OH II I O NH:

0 ON(CH2CH2OH)2 oomomomorm g NHz which was obtained in 25% yield, had amelting 3 point of over 300 C. Nitrogen analysis showed 10.92% N (theoryfor C24H2808N4, N=11.20%). This compound dyed Dacron fiber agreenishblue color which had very good light-fastness on Fade-Ometerexposure.

Example 4 1,4 diamino N,N dimethyl 2,3-anthraquinone-dicarboxamide wasprepared by the method of Example 1 from 22 parts of1,4-diamino-2,3-anthraquinone-dicarboxylic acid, 32 parts of thionylchloride and 220 parts of orthodichlorobenzene. In this example,methylamine was passed into the reaction mixture instead of ammonia. The1,4-diamino-2,3-anthraquinonedicarboxamide of the formula:

NH: N

CONHCHa coNHom g NH:

was obtained in nearly quantitative yield. The compound dyed Dacronfiber a greenish-blue color which had good light fastness on Fade-Ometer exposure.

Instead of the ammonia. or other amine employed in the specific examplesabove given, any of the alkylamines or hydroxy-alkylamines such asethylamine, the propylamines, butylamines, dimethylamine,ethylethanolamine, methylpropylamine or mixtures of any of the aminesmay be substituted therefor to produce compounds which dye the newpolyethylene terephthalate fiber in blue shades having goodlight-fastness properties.

Instead of the particular solvents such as nitrobenzene orortho-dichlorobenzene, any obvious equivalent thereof such aschlorobenzene, trichlorobenzene or other inert organic solvents having aboiling point sufficiently high to permit temperatures such as thoseillustrated in the examples, may of course be employed.

These 1,4 diamino 2,3 anthraquinone dicarboxamides all exhibitsufficiently good affinity and penetration for the new polyester fiberto make them commercially useful for that purpose.

Their fastness to light when applied to this new U C ONH2 ll 0 NH:

3. The 1,4 diamino 2,3 anthraquinonedicarboxamide of the formula:

10 NET CONIHCHzDzOH CONHCHrhOH O NH:

4'. The 1,4 diamino 2 ,3 anthraquinonedicarboxamide of. the formula:

0 NH2 H C ON(CH CH2OH)2 CON(OH2CH2OH)2 ll 0 I IH2 5. The 1,4 diamino 2,3anthraquinonedicarboxamide of the formula:

CONHCH:

CONHCH:

H O NH:

References Cited in the file of this patent UNITED STATES PATENTS NumberName, Date 1,871,821 Nawiasky et al. Aug. 16, 1932 2,174,245 Krause etal Sept. 26, 1939 2,176,437 Runneet a1 Oct. 17, 1939 2,242,760 Schoelleret a1. May 20, 1941 2,294,968 Ellis et a1 Sept. 8, 1942

1. 1,4-DIAMINO-2,3-ANTHRAQUINONE-DICARBOXAMIDES OF THE GENERAL FORMULA: